U.S. patent application number 12/225295 was filed with the patent office on 2010-09-16 for method for producing (poly) glyceryl ether.
Invention is credited to Atsushi Nagasawa, Akira Saito, Mitsuru Uno.
Application Number | 20100234646 12/225295 |
Document ID | / |
Family ID | 38563330 |
Filed Date | 2010-09-16 |
United States Patent
Application |
20100234646 |
Kind Code |
A1 |
Nagasawa; Atsushi ; et
al. |
September 16, 2010 |
Method For Producing (Poly) Glyceryl Ether
Abstract
The present invention relates to a process for producing a
(poly)glyceryl ether which includes the step of reacting an alcohol
with glycidol under a neutral condition. According to the process
of the present invention, the (poly)glyceryl ether having a narrow
molecular weight distribution can be produced with a high yield in
a simplified manner.
Inventors: |
Nagasawa; Atsushi;
(Wakayama, JP) ; Saito; Akira; (Wakayama, JP)
; Uno; Mitsuru; (Wakayama, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Family ID: |
38563330 |
Appl. No.: |
12/225295 |
Filed: |
March 22, 2007 |
PCT Filed: |
March 22, 2007 |
PCT NO: |
PCT/JP2007/055833 |
371 Date: |
September 18, 2008 |
Current U.S.
Class: |
568/672 |
Current CPC
Class: |
C11D 1/72 20130101; C11D
3/2068 20130101; C07C 41/03 20130101; C08G 65/22 20130101; C08G
65/2609 20130101; C08G 65/2654 20130101; C07C 41/03 20130101; C08G
65/2648 20130101; C07C 41/03 20130101; C07C 43/11 20130101; C07C
43/13 20130101 |
Class at
Publication: |
568/672 |
International
Class: |
C07C 41/03 20060101
C07C041/03 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 31, 2006 |
JP |
2006-099681 |
Claims
1. A process for producing a (poly)glyceryl ether, comprising the
step of reacting an alcohol with glycidol under a neutral
condition.
2. The process according to claim 1, wherein the reaction is
conducted at a temperature of from 100 to 200.degree. C.
3. The process according to claim 1 or 2, wherein the glycidol is
dropped at a rate of 1% by mass/min or less on the basis of a whole
amount of the glycidol to be charged, to react with the
alcohol.
4. The process according to claim 1, wherein the alcohol is a
compound represented by the following general formula (1):
R.sup.1--(OR.sup.2).sub.nO--H (1) wherein R.sup.1 is a hydrocarbon
group having 4 to 24 carbon atoms; R.sup.2 is an alkylene group
having 2 or 3 carbon atoms; and n represents an average
polymerization degree of the oxyalkylene group and is a number of
from 0 to 20.
5. The process according to claim 1, wherein the (poly)glyceryl
ether is a compound represented by the following general formula
(3): R.sup.1--(OR.sup.2).sub.nO--(C.sub.3H.sub.5O.sub.2).sub.m--H
(3) wherein R.sup.1, R.sup.2 and n are the same as defined above;
and m represents an average polymerization degree of the glycerol
residue and is a number of from 1 to 10.
6. A use of the (poly)glyceryl ether produced by the process as
defined in claim 1, for detergents.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a process for producing
(poly)glyceryl ethers.
BACKGROUND OF THE INVENTION
[0002] (Poly)glyceryl ethers exhibit excellent properties as a
nonionic surfactant, and have been used in various applications
such as food, cosmetics, toiletries, agricultural chemicals and
drugs for the purposes of emulsification, solubilization,
dispersion, cleaning, foaming, defoaming, penetration,
antibacterial effect, etc.
[0003] There are conventionally known the following methods (1) to
(6) for producing the (poly)glyceryl ethers.
[0004] (1) Method of reacting an alkyl halide with hydroxyl groups
of (poly)glycerol. However, this method has such a problem that
since a large number of hydroxyl groups present in the
(poly)glycerol are subjected to the reaction, one or more alkyl
groups tend to be added to the obtained (poly)glyceryl ethers.
[0005] (2) Method of reacting an alkyl glycidyl ether with water
and polyglycerol to subject an epoxy ring of the alkyl glycidyl
ether to ring opening. However, this method has such a problem that
one or more alkyl glycidyl ether molecules are reacted.
[0006] (3) Method of adding 1 mol of epichlorohydrin to an
aliphatic alcohol, subjecting the resultant addition product to
dehydrochlorination and ring closure in the presence of an alkali,
and then subjecting the resultant ring-closed product again to ring
opening using diluted sulfuric acid, followed by repeating these
procedures until reaching the aimed polymerization degree. (4)
Method of addition-polymerizing a glycidyl ester with an aliphatic
alcohol, and then subjecting the resultant addition product to
saponification using an alkali to eliminate an acyl group therefrom
(refer to Patent Document 1). (5) Method of reacting an alkyl
glycidyl ether with glycerol to synthesize an alkyl diglyceryl
ether, etherifying hydroxyl groups of the alkyl diglyceryl ether
with an allyl halide, and then converting from the allyl group of
the resultant compound into two hydroxyl groups, followed by
repeating these procedures until reaching the aimed polymerization
degree (refer to Patent Document 2). However, these methods have
problems such as complicated reaction steps and, therefore, are
still unsatisfactory as industrial methods.
[0007] (6) Method of addition-polymerizing glycidol with an
aliphatic alcohol in the presence of a catalyst (refer to
Non-Patent Document 1). However, in this method, when using an acid
as the catalyst, a polymerization reaction between glycidol
molecules tends to proceed, resulting in production of a large
amount of polyglycerol, whereas when using a base as the catalyst,
it tends to be difficult to control a molecular weight distribution
of the obtained product, resulting in production of such a
(poly)glyceryl ether having a broad molecular weight distribution.
In order to suppress these undesirable reactions, there is known
the method of using the alcohol in a large excessive amount
relative to the glycidol. However, this method tends to be
considerably deteriorated in productivity, resulting in
industrially disadvantageous process.
[0008] Patent Document 1: JP 9-188755A
[0009] Patent Document 2: JP 2001-114720A
[0010] Non-Patent Document 1: "GLYCIDOL; Properties, Reactions,
Applications", Kleeman, Axel Dr. Alfred Huthig, Verlag Heidelberg,
1981
SUMMARY OF THE INVENTION
[0011] The present invention relates to a process for producing a
(poly)glyceryl ethers by reacting an alcohol with glycidol under a
neutral condition.
DETAILED DESCRIPTION OF THE INVENTION
[0012] As described above, the conventional methods for producing
(poly)glyceryl ethers are unsatisfactory for producing
(poly)glyceryl ether compounds having a narrow molecular weight
distribution with a high yield in a simplified manner.
[0013] The present invention relates to a process for producing a
(poly)glyceryl ether having a narrow molecular weight distribution
with a high yield in a simplified manner while suppressing
production of by-products such as polymers.
[0014] The present inventors have found that the above conventional
problems can be solved by reacting an alcohol with glycidol under a
neutral condition.
[0015] That is, the present invention relates to a process for
producing a (poly)glyceryl ether which include the step of reacting
an alcohol with glycidol under a neutral condition.
[0016] The process for producing a (poly)glyceryl ether according
to the present invention is characterized by reacting an alcohol
with glycidol under a neutral condition. The (poly)glyceryl ether
described herein means a glyceryl ether having one or more glycerol
residues in a molecule thereof.
[0017] The alcohol used in the present invention is preferably a
compound represented by the following general formula (1):
R.sup.1--(OR.sup.2).sub.nO--H (1)
wherein R.sup.1 is a hydrocarbon group having 4 to 24 carbon atoms;
R.sup.2 is an alkylene group having 2 or 3 carbon atoms; and n
represents an average polymerization degree of the oxyalkylene
group and is a number of from 0 to 20.
[0018] In the general formula (1), R.sup.1 is preferably a linear,
branched or cyclic alkyl group or alkenyl group having 6 to 18
carbon atoms.
[0019] Specific examples of R.sup.1 include butyl, hexyl, heptyl,
octyl, nonyl, decyl, undecyl, dodecyl, myristyl, pentadecyl,
palmityl, stearyl, behenyl, 2-ethylhexyl, hexenyl, heptenyl,
octenyl, nonenyl, decenyl, undecenyl, dodecenyl, myristenyl,
pentadecenyl, palmitenyl, oleyl, linoleyl, linolenyl, arachidyl,
2-ethylhexenyl, cyclopentyl, cyclohexyl and cyclooctyl. Among these
groups, preferred are linear or branched alkyl groups having 6 to
14 carbon atoms, more preferred are linear or branched alkyl groups
having 6 to 12 carbon atoms, and still more preferred are linear
alkyl groups having 6 to 10 carbon atoms.
[0020] Specific examples of R.sup.2 include an ethylene group
(--C.sub.2H.sub.4--) and a propylene group
(--C.sub.3H.sub.6--).
[0021] The suffix n represents an average polymerization degree of
the oxyalkylene group (--OR.sup.2--) and is preferably a number of
from 0 to 8, more preferably from 0 to 6 and most preferably 0.
[0022] In the present invention, the alcohol is reacted with
glycidol represented by the following formula (2). In the reaction,
when using the compound represented by the following general
formula (1) as the alcohol, the (poly)glyceryl ether represented by
the following general formula (3) is produced as shown in the
following reaction formula.
##STR00001##
[0023] In the general formula (3), R.sup.1, R.sup.2 and n are the
same as defined above, and m represents an average polymerization
degree of the glycerol residue and is a number of from 1 to 10.
Also, the preferred ranges of R.sup.1, R.sup.2 and n are the same
as described above, and m is preferably a number of from 1 to 5,
more preferably from 1 to 4, still more preferably from 1 to 3, and
most preferably 1.
[0024] The glycerol residue used herein means a group represented
by the formula: --CH.sub.2--CH(OH)--CH.sub.2O-- and/or a group
represented by the formula: --CH.sub.2--CH(CH.sub.2OH)--O--.
[0025] In the present invention, the reaction between the alcohol
and glycidol is conducted under a neutral condition. The "neutral
condition" used herein means that the pH of the reaction system
lies within the range of from 6 to 8, preferably from 6.5 to 7.5
and more preferably from 6.5 to 7.0, but is not limited to only the
case where the pH of the reaction system is 7.
[0026] The method of conducting the above reaction under a neutral
condition is not particularly limited, and there may be used, for
example, the method of using high-purity compounds as the raw
alcohol and glycidol, or the method of using such raw materials
from which acid substances derived from the raw materials are
removed. When the acid substances are contained in the raw
materials to such an extent that the pH of the reaction system is
adversely affected thereby, commercially available pH controllers
may be added thereto.
[0027] The "pH of the reaction system" used herein means the value
determined by mixing a mixed solution prior to adding glycidol
thereto with an equal amount of ion-exchanged water to separate a
water layer therefrom, and then measuring the pH of the thus
separated water layer.
[0028] The ratio between amounts of the alcohol and glycidol used
is not particularly limited, and is suitably controlled such that
the molar ratio of glycidol to the alcohol (glycidol/alcohol) is
preferably from 0.001 to 4, more preferably from 0.001 to 1, still
more preferably from 0.01 to 0.8, further still more preferably
from 0.05 to 0.6, and further still more preferably from 0.2 to
0.5.
[0029] In the present invention, a catalyst may or may not be used.
The catalyst may be used as long as the reaction system is still
kept in a neutral condition even when adding the catalyst thereto.
Examples of the catalyst include acid catalysts such as Lewis acids
and basic catalysts such as metal alcoholates. The reaction is more
preferably conducted in the absence of any catalyst.
[0030] More specifically, in the preferred reaction, the alcohol is
charged into a reactor, and then glycidol is added to the reactor
without adding any catalyst thereto, thereby allowing these
compounds to be reacted with each other under a neutral
condition.
[0031] The reaction between the alcohol and glycidol is an
exothermic reaction. Therefore, the reaction is preferably
gradually carried out by continuously dropping glycidol to the
alcohol or intermittently adding divided parts of glycidol thereto,
while stirring the alcohol.
[0032] The dropping rate of glycidol is preferably 10% by mass/min
or less, more preferably 2% by mass/min or less, still more
preferably 1% by mass/min or less, further still more preferably
0.75% by mass/min or less, and further still more preferably 0.5%
by mass/min or less on the basis of a whole amount of glycidol to
be charged. The lower limit of the dropping rate of glycidol is
preferably 0.1% by mass/min or more.
[0033] When intermittently adding divided parts or installments of
glycidol to the alcohol, the amount of glycidol to be added is
equally divided into preferably four or more parts, more preferably
6 or more parts and still more preferably 8 or more parts, and the
divided parts or installments of glycidol are added to the alcohol
at equal intervals such that the addition rate (dropping rate)
thereof falls within the above specified range as a whole.
[0034] The time required for continuously dropping glycidol or
intermittently adding divided parts of glycidol, varies depending
upon the amount of glycidol to be added, etc., and is preferably
from 0.25 to 24 h, more preferably from 1 to 10 h and still more
preferably from 2 to 5 h from the industrial viewpoints.
[0035] In addition, after completing the addition of glycidol, the
reaction system may be kept under the same condition over a period
of from 0.1 to 3 h for aging thereof.
[0036] The reaction temperature is preferably from 100 to
200.degree. C., more preferably from 130 to 180.degree. C. and
still more preferably from 145 to 165.degree. C. from a good
reaction efficiency. When the reaction temperature is too low, the
reaction tends to proceed too slowly. When the reaction temperature
is too high, the side reactions such as polymerization between
glycidol molecules tend to undesirably occur.
[0037] In addition, the reaction conducted under a solvent-free
condition is excellent from the viewpoint of a good industrial
convenience. However, when the reaction system is in a highly
viscous state or non-uniform state, the reaction may be conducted
in the presence of an adequate amount of a suitable solvent.
[0038] Examples of the solvent include amphipatic solvents such as
tetrahydrofuran, dioxane and ethylene glycol dimethyl ether;
hydrocarbon-based solvents, e.g., aliphatic hydrocarbons such as
hexane, heptane, cyclohexane, methyl cyclohexane, isooctane and
hydrogenated triisobutylene, and aromatic hydrocarbons such as
benzene, toluene, xylene and ethyl benzene; and silicone-based
solvents such as octamethyl cyclotetrasiloxane and decamethyl
cyclopentasiloxane. Meanwhile, these solvents are preferably
subjected to dehydration or deaeration upon use.
[0039] The alkyl (poly)glyceryl ether obtained in the process of
the present invention is useful as a nonionic surfactant, and its
applications as well as its configurations upon use are not
particularly limited. For example, the alkyl (poly)glyceryl ether
may be used in the form of a single compound, an aqueous solution,
a water dispersion, an emulsion containing the other oil phase, a
hydrous gel, an alcohol solution, a dispersion, or a mixture with
solid substances such as an oil-based gel or waxes, as well as in a
wet or infiltrated, or penetrated condition or configuration.
[0040] The alkyl (poly)glyceryl ether obtained in the process of
the present invention may be extensively used, for example, as
emulsifiers, solubilizers, dispersants, detergents, foaming agents,
defoaming agents, penetrants, antibacterial agents, etc., for the
purposes of emulsification, solubilization, dispersion, cleaning,
foaming, defoaming, penetration, antibacterial effect, etc., in
various applications such as food, cosmetics, toiletries,
detergents, agricultural chemicals and drugs. In particular, the
alkyl (poly)glyceryl ether obtained in the process of the present
invention is excellent as a material for detergents.
Examples
[0041] In the following Examples and Comparative Examples, the
terms "%" and "ppm" represent "% by mass" and "ppm by mass",
respectively.
Example 1
[0042] A 300 mL four-necked flask equipped with a stirrer, a
nitrogen feed pipe and a thermometer was charged with 102.2 g of
hexyl alcohol (available from Sigma-Aldrich Japan K.K.). At this
time, the pH of the content in the flask was 6.7. Thereafter, while
maintaining the reaction system in the flask at 150.degree. C.,
22.2 g of glycidol (available from Nacalai Tesque, Inc.; purified
by distillation prior to the use) was dropped into the flask over 4
h (molar ratio of glycidol to alcohol (glycidol/alcohol)=0.3).
After completion of the dropping, the contents of the flask were
reacted at 150.degree. C. over 58 h, thereby obtaining hexyl
polyglyceryl ether. As a result of subjecting the obtained product
to quantitative determination by gas chromatography, it was
confirmed that the obtained hexyl polyglyceryl ether was composed
of 41.0 g (83.7%) of hexyl glyceryl ether, 6.1 g (12.4%) of hexyl
diglyceryl ether, 0.8 g (1.6%) of hexyl triglyceryl ether, and 2.3%
of unknown components.
Comparative Example 1
[0043] A 300 mL four-necked flask equipped with a stirrer, a
nitrogen feed pipe and a thermometer was charged with 102.2 g of
hexyl alcohol and 0.35 g of potassium methoxide, followed by
stirring the contents in the flask at 90.degree. C. over 2 h. At
this time, the pH of the contents in the flask was 12.2.
Thereafter, while maintaining the reaction system in the flask at
90.degree. C., 7.4 g of glycidol (molar ratio of glycidol to
alcohol (glycidol/alcohol)=0.1) was equally divided into three
parts, and the individual parts were intermittently added into the
flask at intervals of 4 h. Then, the contents in the flask were
reacted at 90.degree. C. for 2 h, thereby obtaining hexyl
polyglyceryl ether. As a result of subjecting the obtained product
to quantitative determination by gas chromatography, it was
confirmed that the obtained hexyl polyglyceryl ether was composed
of 6.8 g (49.4%) of hexyl glyceryl ether, 2.4 g (17.4%) of hexyl
diglyceryl ether, 1.0 g (7.2%) of hexyl triglyceryl ether, and
26.0% of unknown components.
Comparative Example 2
[0044] A 300 mL four-necked flask equipped with a stirrer, a
nitrogen feed pipe and a thermometer was charged with 102.2 g of
hexyl alcohol and 0.14 g of boron trifluoride (47% ether solution).
At this time, the pH of the contents in the flask was 2.0. While
maintaining the reaction system in the flask at 50.degree. C., 22.2
g of glycidol (molar ratio of glycidol to alcohol
(glycidol/alcohol)=0.3) was equally divided into three parts, and
the individual parts were intermittently added into the flask at
intervals of 4 h. Then, the contents in the flask were reacted at
50.degree. C. for 2 h, thereby obtaining hexyl polyglyceryl ether.
As a result of subjecting the obtained product to quantitative
determination by gas chromatography, it was confirmed that the
obtained hexyl polyglyceryl ether was composed of 32.0 g (69.4%) of
hexyl glyceryl ether, 10.1 g (21.9%) of hexyl diglyceryl ether, 2.9
g (6.3%) of hexyl triglyceryl ether, and 2.4% of unknown
components.
TABLE-US-00001 TABLE 1 Monoglycerol Diglycerol Triglycerol Unknown
compound compound compound components Example 1 83.7% 12.4% 1.6%
2.3% Comparative 49.4% 17.4% 7.2% 26.0% Example 1 Comparative 69.4%
21.9% 6.3% 2.4% Example 2
[0045] From Table 1, it was confirmed that in Example 1, the
monoglycerol compound was produced with a higher selectivity as
compared to those obtained in Comparative Examples 1 and 2.
INDUSTRIAL APPLICABILITY
[0046] In the production process of the present invention, a
polyglyceryl ether, in particular, a monoglycerol compound, having
a narrow molecular weight distribution can be produced with a high
yield in a simplified manner while suppressing production of
by-products such as polymers.
* * * * *